Underlayer composition for promoting self assembly and method of making and using

ABSTRACT

Disclosed herein is an underlayer composition, wherein the underlayer is typically used for promoting the formation of self assembled structures, and wherein the underlayer formulation comprises: (a) a polymer comprising at least one monomer repeat unit having the structure (I) 
     
       
         
         
             
             
         
       
     
     wherein X is a crosslinking group chosen from 
     
       
         
         
             
             
         
       
     
     and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C 1 -C 4 alkyl or tri (C 1 -C 4 alkyl)silyl; (b) at least one thermal acid generator; and (c) a solvent. The invention further relates to methods of making and using the composition.

FIELD OF THE INVENTION

The present application for patent is in the field of lithographic patterning by directed self assembly and more specifically in the area of energy neutral and pinning under-layers that support the formation of self assembled features.

BACKGROUND

In recent years, directed self assembly has emerged as a useful means of organizing solution-synthesized nanostructures to create lithographic features and for a wide variety of other applications. For example see Thurn-Albrecht et al., “Ultrahigh Nanowire Arrays Grown in Self-Assembled. Diblock Copolymer Templates”, Science, 290, 2126, (2000). Black et al., “Integration of Self-Assembled Diblock Copolymers for Semiconductor Capacitor Fabrication,” Applied Physics Letters, 79, 409, (2001) and Akasawa et al., “Nanopatterning with Microdomains of Block Copolymers for Semiconductor Capacitor Fabrication,” Jpn. J. Appl. Phys., 41, 6112, (2002).

In many directed self assembly applications, molecular interactions drive phase separation into domains; wherein immiscible polar and nonpolar materials are concentrated. Of particular interest in directed self assembly applications are thin films of block copolymers that have polar and nonpolar blocks said blocks having predetermined sizes corresponding to their individual molar masses. These blocks of selected size render domains with a natural length scale associated with their respective molar masses and compositions. Further, by tuning the molar masses of the individual blocks within block copolymers, one can generate various morphologies with selected sizes, such as lamellae or cylinders of a specific width, specific pitch and specific symmetry patterns such as hexagonal close packed arrays or parallel lines.

Film layers made with energy neutral polymers (hereinafter, neutral layers) are sometimes used because they do not show preferred wetting for one of the polymer blocks over another and, therefore, tend not to enforce or guide, preferentially, the formation of a particular domain at a particular location. Neutral layers may be, functionalized polymer brushes, random copolymers having similar repeat units to those used in the block copolymer being used or blends of homopolymers, each respectively having similar monomers to those in the block copolymer being used.

Pinning layers are film layers made with polymers having a predominance of similar monomers to those in one of the blocks. These are sometimes used because they do show a preferred wetting for one of the polymer blocks over another and, therefore, tend to enforce or “pin,” preferentially, the formation of a particular domain at a particular location.

Among the methods used to guide self-assembly in thin films of block copolymers are graphoepitaxy and chemical epitaxy. In graphoepitaxy self-assembly is guided by pre formed topographical structures such as trenches. For example, a topographically patterned substrate with a neutral underlying surface and with sidewalls that are preferentially attracted to one type of the block copolymer domain (for example, the A domains of an A-B diblock copolymer assembly) can be used to direct self-assembly inside the trench through topographical confinement. With a trench of width L and a block copolymer (BCP) having a periodicity of P_(BCP), frequency multiplication of a factor of L/P_(BCP) can be achieved for the remaining domain.

Various attempts have been made to incorporate crosslinking functionality into either a pinning layer or a neutral layer; the activation of which crosslinks the underlayer and retards comingling between the underlayer and the block copolymer. For example, in U.S. Pat. No. 8,226,838, Cheng et al. disclose an underlayer comprising “a cross linked organic polymer including an epoxy-based homopolymer or copolymer.” wherein epoxy based monomer repeat units include epoxydicyclopentadienyl methacrylate, glycidyl (meth)acrylate, 2,3-epoxycyclohexyl (meth)acrylate, (2,3-epoxycyclohexyl)methyl (meth)acrylate, 5,6-epoxynorbornene (meth)acrylate, and combinations comprising at least one of the foregoing. The epoxy based monomers are copolymerized with various other monomers, including styrene and methyl methacrylate, alone or in combination to provide, respectively, pinning layers or neutral layers as required. However, while the monomer repeat units listed above may work to provide a crosslinked substrate, they are less than effective in matching the interaction properties of monomers such as methyl methacrylate.

Therefore, there remains a need for polymer compositions that provide thermally crosslinkable curing and, at the same time provide surface interaction characteristics that resemble styrenic monomer repeat units.

SUMMARY OF THE INVENTION

The present invention relates to a formulation for depositing an underlayer for promoting the formation of self assembled structures. The underlayer comprises: (a) a polymer comprising at least one monomer repeat unit having the structure (I)

wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄ alkyl, tri (C₁-C₄alkyl)silyl; (b) at least one thermal acid generator; and (c) a solvent. The invention further relates to methods of making and using the novel composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1( a) is a scanning electron micrograph of a block copolymer film prepared as described in Example 4. FIG. 1( b) is a scanning electron micrograph of a block copolymer film prepared as described in Example 5.

FIG. 2 relates to a process for directed self assembly of a block copolymer.

FIG. 3 relates to another process for directed self assembly of a block copolymer.

DETAILED DESCRIPTION

As used herein, the conjunction “and” is intended to be inclusive and the conjunction “or” is not intended to be exclusive unless otherwise indicated or made clear or necessary by context. For example, the phrase “or, alternatively” is intended to be exclusive. Further, for example, the conjunction “or” is understood to be exclusive when describing chemical substitution on a single site. The articles “a” and “the” as used herein are understood to encompass the plural as well as the singular. As used herein, the term “copolymer” is understood to comprise two or more monomer repeat units and a “polymer” may be a homopolymer, or a copolymer. As used herein, when the prefix, “(meth)acryl” is used, “acryl” or “methacryl” is intended. For example, (meth)acrylate may represent an acrylate or a methacrylate. As used herein, the adjective, “exemplary” is intended to mean illustrative of a characteristic, without expressing preference. As used herein, the term “monomer repeat unit” or, simply, “monomer,” is used to describe the unreacted monomer or the reacted unit within the polymer. The term ‘formulation’ and ‘composition’ is used interchangeably.

Disclosed herein is a novel underlayer formulation, wherein the underlayer is typically used for promoting the formation of self assembled structures, and wherein the underlayer formulation comprises: (a) a polymer comprising at least one monomer repeat unit having the structure (I)

wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄alkyl or tri (C₁-C₄alkyl)silyl; (b) at least one thermal acid generator; and (c) a solvent. Structure (I) is defined as the monomer which is polymerized to obtain the resultant repeat unit in the polymer. The polymer of the novel underlayer formulation can be a random copolymer.

Further disclosed herein is a process for producing a formulation for depositing a cured underlayer for promoting the formation of self assembled structures, wherein the process comprises: (a) agitating a mixture, comprising (i) a polymer comprising at least one monomer repeat unit having the structure (I), supra, wherein X is a crosslinking group chosen from (II), (III), (IV), or (V), supra, and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄ alkyl, tri (C₁-C₄alkyl)silyl; (ii) at least one thermal acid generator; and (iii) a solvent; whereby a homogenous solution is produced; and (b) filtering the resulting homogeneous solution with a filter.

Still further disclosed herein is a process for directing a multiplied pattern in a block copolymer film, wherein the process comprises: (a) providing a block copolymer having two or more spontaneously separating blocks; (b) providing a substrate; (c) coating, on the substrate, a first formulation for depositing a neutral layer and thermally curing the neutral layer; (d) disposing the block copolymer on at least a portion of the cured neutral layer; wherein the first formulation comprises (i) a polymer comprising at least one monomer repeat unit having the structure (I); wherein X is a crosslinking group chosen from the structures (II), (III), (IV) or (V); and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄alkyl, tri (C₁-C₄alkyl)silyl; at least one thermal acid generator; and (iii) a solvent.

In another embodiment, the process for directing a multiplied pattern in a block copolymer, above, further comprises the steps of (e) before disposing the block copolymer, forming a pattern in the neutral layer by a lithographic process; (f) providing a pinning material in the pattern from a second formulation; and thermally curing the pinning material; wherein the second formulation comprises: (i) a polymer comprising at least one monomer repeat unit having the structure, (I); and wherein X is a crosslinking group chosen from (II), (III), (IV), or (V); and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄alkyl, tri (C₁-C₄alkyl)silyl; (ii) at least one thermal acid generator; and (iii) a solvent.

In still another embodiment, of the process for directing a multiplied pattern in a block copolymer film, the first coating may be a pinning layer and the second coating may be a neutral layer.

In still another embodiment, of the process for directing a multiplied pattern in a block copolymer film, the first coating may be a neutral layer and the second coating may be a pinning layer.

The second coating may be a brush neutral polymer or a brush pinning polymer. Examples of the second layer can be OH-brush neutral polymer such as PMMA-r-PS—OH with PS from 45-80 mol %; OH-brush pinning polymer, such as 100% PS—OH; and a second formulation comprising (i) a second polymer comprising at least one pendant vinyl ether monomer repeat unit having the structure (I), wherein R is chosen from H, C₁-C₄ alkyl, or halogen, and W is a divalent group chosen from C₁-C₆ alkylene, C₆-C₂₀ arylene, benzylene, or C₂-C₂₀ alkyleneoxyalkylene.

The novel formulations of the above disclosures are suitably assembled by dissolving one or more components in a suitable solvent and agitating until a homogeneous mixture is obtained. Herein, it is understood that the one or more components may be dissolved separately and the separate solutions blended together to give the formulation. Alternatively, two or more of the individual components may be mixed together with a solvent and finally blended (if required). For example, the polymer and the thermal acid generator may be dissolved separately in their respective solvents, which may be the same or different, and the resulting solutions blended and agitated to obtain a homogeneous solution. As a further example, the polymer and the thermal acid generator can be added to a solvent or solvent mixture and agitated until a homogeneous solution is obtained.

Further, it may be advantageous to filter the resulting solutions to exclude fine particles. The required size rating of the filter may depend on the application and other requirement s such as cost. For example, it may be advantageous to filter the formulation through a filter rated at less than or equal to 200 nm (nanometers). As a further example, it may be advantageous to filter the formulation through a filter rated at less than or equal to 100 nm (nanometers). As a still further example, it may be advantageous to filter the formulation through a filter rated at less than or equal to 40 nm (nanometers). As a further example, it may be advantageous to filter the formulation through a filter rated at less than or equal to 10 nm (nanometers). As a further example, it may be advantageous to filter the formulation through a filter rated at less than or equal to 5 nm (nanometers). It also may be advantageous to subject the solution to a staged filtration, using a filter train having filters of decreasing pore size. Depending on the solvent and formulation components, and without limitation, filters may be constructed of symmetrical or asymmetrical ultra high density polyethylene, nylon, poly(tetrafluoroethylene), poly(vinylidine fluoride), hexafluoropropylene, perfluoropropylvinylether, perfluoromethylvinylether, or the like. Suitable filters may be obtained from Entegris, Inc. of Billerica, Mass.

Thermal acid generators are known to produce acids upon heating. Such acids may be Lewis acids or Brønsted acids. The latter acids may be characterized by their corresponding anion. Accordingly, thermal acid generators may produce acids having anions such as, without limitation, p-toluene sulfonate, dodecylbenzene sulfonate, perfluoro alkane sulfonates, perfluorinated and partially fluorinated alkoxy alkane sulfonates, benzene sulfonate and fluorinated benzene sulfonates, alkane sulfonates, camphor sulfonate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrafluoroborate, halogenides, phosphonates, and the like.

The anions of thermal acid generators may without limitation, be paired with groups that serve as counterions such as sulfonium or iodonium salts, ammonium salts, and ammonium salts of primary, secondary or tertiary amines. In addition, the anionic moieties may be covalently bonded as an ester or other linkage. For example thermal acid generators may be o-nitrobenzyl or p-nitrobenzyl esters, 5-norbornene-2,3-dicarboximidyl-N-esters such as 5-norbornene-2,3-dicarboximidyl-N-trifluoromethane sulfonate or other dicarboximidyl esters such as 1,3-dioxoisoindolin-2-yl-esters, or 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl esters, oxime esters such as oxime sulfonates such as (Z)-2,2,2-trifluoro-1-phenylethanone O-trifluoromethylsulfonyl oxime, as described in U.S. Pat. No. 6,512,020 to Asakura et al. Further, alkane sulfonates may be used as thermal acid generators. In general, oxo-acid anions such as sulfonates may be esterified or used as salts, while non-oxo-acid anions such as tetrafluoroborate may be used as salts such as trimethylammonium tetrafluoroborate. Moreover, the thermal acid generator may comprise a substituted or unsubstituted halogenated alkyl compound.

Exemplary thermal acid generators may include, without limitation, the onium salts, halogen containing compounds, perfluorobenzene sulfonate esters, perfluoroalkane sulfonate esters. Without limitation, exemplary thermal acid generators for the above formulation include tri-C₁-C₈-alkylammonium p-toluenesulfonate, tri-C₁-C₈-alkylammonium dodecylbenzenesulfonate, tri-C₁-C₈-alkylammonium perfluorobutane-1-sulfonate, tri-C₁-C₈-alkylammonium trifluoromethane-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, bis(4-t-butyl phenyl)iodonium trifluoromethane sulfonate, bis(4-t-butyl phenyl)iodonium perfluoro-1-butanesulfonate, bis(4-t-butyl phenyl)iodonium perfluoro-1-octanesulfonate, bis(phenyl)iodonium hexafluoroantimonate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing. Examples include, without limitation, ammonium salts of primary, secondary or tertiary amines. In certain applications, it may be desirable to exclude some types of thermal acid generators because of their high temperature characteristics or because they may leave undesirable byproducts behind that could lead to defects, particularly in a neutral layer or a pinning layer. Examples of these may include sulfonium or iodonium salts. Without intending to be bound by theory, it is believed that at least some of these byproducts derive from uncontrolled free radical reactions within the film. In contrast, other thermal acid generators of the “latent acid” variety create volatile byproducts that tend to evaporate from the film during baking. The thermal acid generator is capable of generating a strong acid upon heating. The thermal acid generator (TAG) used in the present invention may be any one or more that upon heating generates an acid which can react with the polymer and propagate crosslinking of the polymer present in the invention, particularly preferred is a strong acid such as a sulfonic acid. Preferably, the thermal acid generator is activated at above 90° C. and more preferably at above 120° C., and even more preferably at above 150° C. Examples of thermal acid generators are ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium salts of strong non nucleophilic acids. Also, covalent thermal acid generators are also envisaged as useful additives for instance 2-nitrobenzyl esters of alkyl or arylsulfonic acids and other esters of sulfonic acid which thermally decompose to give free sulfonic acids. Examples are quaternary ammonium perfluoroalkylsulfonate. Examples of labile esters: 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate, 2-trifluoromethyl-6-nitrobenzyl 4-nitro benzenesulfonate; phenolic sulfonate esters such as phenyl, 4-methoxybenzenesulfonate; quaternary ammonium tris(fluoroalkylsulfonyl)methide, and quaternaryalkyl ammonium bis(fluoroalkylsulfonyl)imide, alkyl ammonium salts of organic acids, such as triethylammonium salt of 10-camphorsulfonic acid. A variety of aromatic (anthracene, naphthalene or benzene derivatives) sulfonic acid amine salts can be employed as the TAG, including those disclosed in U.S. Pat. Nos. 3,474,054, 4,200,729, 4,251,665 and 5,187,019. Preferably the TAG will have a very low volatility at temperatures between 170-220° C. Examples of TAGs are those sold by King Industries under Nacure and CDX names. Such TAG's are Nacure 5225, and CDX-2168E, which is a dodecylbenzene sulfonic acid amine salt supplied at 25-30% activity in propylene glycol methyl ether from King Industries, Norwalk, Conn. 06852, USA.

Suitable solvents for the formulations and synthesis procedures described herein include glycol ether acetates, esters, α-hydroxy esters, α-alkoxy esters alcohols, ketones, amides, imines, ethers, ether esters, ether alcohols and the like. Specifically, solvents may include, without limitation, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, 3-methoxymethyl propionate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethylsulfoxide, γ-butyrolactone, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, butanone, 2-pentanone, 2-hexanone, 2-heptanone, and tetramethylene sulfone. The solvents may be used alone or as mixtures.

The above formulation may further comprise suitable thermal curing agents that include, but are not limited to, imidazoles, primary, secondary, and tertiary amines, quaternary ammonium salts, anhydrides, polysulfides, polymercaptans, phenols, carboxylic acids, polyamides, quaternary phosphonium salts, and combinations thereof.

The polymers herein, whether pinning layers or neutral layers, may be pure polymers or blends. The polymers can be random polymers. Moreover, the polymers may be blended with oligomers, monomers or other small molecules such as leveling agents, dissolution modifiers, flexiblizers, plasticizers and the like. In addition, the polymers may be, a telechelic polymers which, without limitation may be monofunctional or difunctional, and wherein the functional group(s) at the end of the polymer chains may be, without limitation, chosen from an alcohol group, an ester group, a carbonate group, a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, an amine group, an amide or imide group, an epoxy group, a silyl group, an alkoxysilyl group, an alkylsilyl group, an aminosilane group, an isocyanate group, a thiocyanate group, or an isothiocyanate group. The monomer repeat units in the pinning materials and neutral materials may be the same or similar to those in one of the blocks in the selected block copolymer. For example, if the selected block copolymer is (b)-polystyrene-(b)-polymethylmethacrylate, the pinning material could comprise polystyrene or polymethyl methacrylate or polymers having similar repeat units such as poly-4-methylstyrene or polymethyl acrylate. The molecular weight of the polymers disclosed herein may be, for example 800-500,000 Daltons. As a further example, the molecular weight of the polymer in the pinning material may be between 2,000-200,000 Daltons. As a still further example, the molecular weight of the polymer in the pinning material may be between 10,000-100,000 Daltons.

In addition to the substituted styrene repeat unit of structure (I), polymers disclosed herein may comprise other monomer repeat units. These include, without limitation, C₁-C₁₀ alkyl (meth)acrylate, styrene, vinyl pyridine (e.g. 2-vinyl pyridine, 4-vinyl pyridine), butadiene, isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 4-hydroxystyrene, isobornyl methacrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.

Further, in addition to the substituted styrene repeat unit of structure (I), polymers disclosed herein may comprise monomer repeat unit combinations such as methyl (meth)acrylate and styrene, butadiene and butyl (meth)acrylate, butadiene and dimethyl siloxane, butadiene and methyl(meth) acrylate, butadiene and vinyl pyridine, isoprene and methyl(meth) acrylate, isoprene and vinyl pyridine, butyl (meth)acrylate and methyl(meth)acrylate, butyl (meth)acrylate and vinyl pyridine, hexyl(meth)acrylate and vinyl pyridine, isobutylene and butyl (meth)acrylate, isobutylene and dimethylsiloxane, isobutylene and methyl (meth)acrylate, isobutylene and vinyl pyridine, isoprene and ethylene oxide, butyl (meth)acrylate and vinyl pyridine, ethylene and methyl (meth)acrylate, methyl (meth)acrylate and butyl (meth)acrylate, styrene and butadiene, styrene and butyl (meth)acrylate, styrene and dimethylsiloxane, styrene and isoprene, styrene and vinylpyridine, ethylene and vinyl pyridine, vinyl pyridine and methyl (meth)acrylate, ethylene oxide and isoprene, ethylene oxide and butadiene, ethylene oxide and styrene, ethylene oxide and methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and butadiene, 2-hydroxyethyl (meth)acrylate and butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and dimethyl siloxane, 2-hydroxyethyl (meth)acrylate and ethylene, 2-hydroxyethyl (meth)acrylate and hexyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate and isobutylene, 2-hydroxyethyl (meth)acrylate and isoprene, 2-hydroxyethyl (meth)acrylate and styrene, 2-hydroxyethyl (meth)acrylate and vinyl pyridine, (meth)acrylonitrile and butadiene, (meth)acrylonitrile and butyl (meth)acrylate, (meth)acrylonitrile and dimethyl siloxane, (meth)acrylonitrile and ethylene oxide, (meth)acrylonitrile and ethylene, (meth)acrylonitrile and hexyl(meth)acrylate, (meth)acrylonitrile and 2-hydroxyethyl (meth)acrylate, (meth), acrylonitrile and isobutylene, (meth)acrylonitrile and isoprene, (meth)acrylonitrile and methyl (meth)acrylate, (meth)acrylonitrile and styrene, or (meth)acrylonitrile and vinyl pyridine.

Polymerization may be initiated by free radical methods (where appropriate) as disclosed in March, (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.). Initiators may include, without limitation, halogen dimers, azo compounds, such as azobisisobutyronitrile (AIBN), and 1,1′-azobis(cyclohexanecarbonitrile) (ABCN), and organic peroxides such as di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl peroctoate, and acetone peroxide. Numerous other initiators are available from Akzo Nobel Polymer Chemicals LLC, of Chicago, Ill.

Further, and without limitation, polymerization may also be initiated by controlled/“living” radical polymerization techniques such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization and nitroxide-mediated polymerization (NMP) as disclosed in September, 2009, Controlled and Living Polymerizations: From Mechanisms to Applications (Wiley-VCH).

Further, and without limitation, polymerization may also be initiated by anionic polymerization methods (where appropriate), using initiators such as lithium alkyl compounds, lithium or sodium biphenyl, lithium or sodium anthracene, sodium amide, potassium amide, alkalai metal acrylonitrile adducts and the like. In addition, polymerization can occur using a combination of anionic and free radical polymerization, as disclosed in Japanese Patent Publication No. 58-225103 to Yokota.

Further, and without limitation, polymerization may also be initiated by cationic polymerization methods (where appropriate), using initiators such as without limitation, aluminum chloride, boron trifluoride, antimony pentachloride, titanium tetrachloride, zinc chloride, and alkyl aluminum dichloride. In addition, combinations such as aluminum chloride and tert-butyl chloride may be used to generate the tert-butyl carbocation.

Block copolymers useful for forming self-directed assembly may be made by anionic polymerization or other polymerization methods known in the art. Exemplary block copolymer assembly components that are contemplated for use in the present method also include a combination comprising at least one block copolymer. The block copolymer can be di-block copolymer as well as multi-block copolymer. Exemplary di-block copolymers include, without limitation, poly(styrene-b-vinyl pyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene), poly(styrene-b-methylmethacrylate), poly(styrene-b-alkenyl aromatics), poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene-propylene)), poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide), poly(styrene-b-t-butyl(meth)acrylate), poly(methyl methacrylate-b-t-butylmethacrylate), poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly((styrene-alt-maleic anhydride)-b-styrene), poly(styrene-b-dimethylsiloxane), and poly(styrene-b-dimethylgermanium oxide). Exemplary tri-block copolymers include poly(styrene-b-methyl methacrylate-b-styrene), poly(methyl methacrylate-b-styrene-b-methyl methacrylate), poly((styrene-alt-maleic anhydride)-b-styrene-b-methyl methacrylate), poly(styrene-b-dimethylsiloxane-b-styrene), and poly(ethylene oxide-b-isoprene-b-styrene). An exemplary multi-block copolymer is poly(styrene-b-methyl methacrylate) n, where n is greater than 1. It will be understood that the foregoing exemplary block copolymers are only intended to be illustrative and should not be considered as limited thereto.

The block copolymer can have an overall molecular weight and polydispersity (pd) amenable to the film forming steps disclosed herein, such that formation of spontaneously separating blocks in the block copolymer assembly can proceed thermally or thermally under conditions that may assist phase separation such as a solvent vapor atmosphere. In an embodiment, the block copolymer may have a number averaged molecular weight (Mn) of 1,000 to 200,000 g/mol. Molecular weight, both Mw and Mn, can be determined by, for example, gel permeation chromatography using a universal calibration method, calibrated to polystyrene standards. In a further embodiment each block in the block copolymer may separately have a molecular weight (Mn) of 250 to 175,000 g/mol. In a further embodiment, each block in the block copolymer may separately have a polydispersity (Mw/Mn) between 1.0 and 2.0. In a still further embodiment, each block in the block copolymer may separately have a polydispersity (Mw/Mn) between 1.0 and 1.5. In a still further embodiment, each block in the block copolymer may separately have a polydispersity (Mw/Mn) between 1.0 and 1.5. In a still further embodiment, each block in the block copolymer may separately have a polydispersity (Mw/Mn) between 1.0 and 1.1.

Lithographic processes used to image polymer layers may include patterning using methods and radiation types known in the art. These include photon beams having wavelengths in the x-ray, soft-x-ray, extreme ultraviolet, vacuum ultraviolet or ultraviolet ranges, electron beams, or ion beams. Photoresists known in the art may suitably be used in conjunction with the chosen radiation to form a pattern on cured polymer films. Such patterns may be etched into the cured polymer films using a variety of etching techniques such as plasma etching, reactive ion etching, ion milling, or other methods known in the art. The manner of producing a lithographically defined image is not critical and other techniques may be used without departing from the scope of the claims appended hereto.

The substrate on which the processes described herein may be practiced includes any substrate normally encountered in a semiconductor fabrication process. Such substrates include, without limitation, semiconductor substrates such as silicon or silicon-germanium, metal substrates such as aluminum or copper, compound substrates such as silicon dioxide, silicon nitride, silicon oxynitride, tantalum silicide, titanium silicide, titanium nitride, tantalum nitride, or polymers such as antireflective coatings.

Any process useful for self assembly of block copolymers using the novel composition as a neutral or pinning layer is within the scope of the present invention. FIG. 2 discloses one of the useful processes where the novel composition is coated on a substrate (1) and then cured to form a pinning layer (2); the pinning layer is then patterned using a lithographic process with photoresist (3) to form a patterned pinning layer (4); the patterned pinning layer is further coated with a second coating of a neutral layer (5) and rinsed with a rinsing solution thereby depositing the second coating only in the openings of the patterned pinning layer; the block copolymer (6) is then coated over the pinning patterned layer with the second coating and heated to self-assemble the block copolymer. The self-assembled block copolymer is then dry or wet etched to form a pattern (7).

FIG. 3 discloses another process where the novel composition is coated on a substrate (1) and then cured to form a neutral layer (2), the neutral layer is then patterned using a lithographic process with photoresist (3) to form a patterned neutral layer (4); optionally, the patterned neutral layer is further coated with a second coating of a pinning layer (5) and rinsed with a rinsing solution thereby depositing the second coating only in the openings of the neutral layer; the block copolymer (6) is then coated over the neutral patterned layer with the second pinning coating and heated to self-assemble the block copolymer (7). The self-assembled block copolymer is then dry or wet etched to form a pattern.

The substituted styrene monomer repeat units disclosed herein may be synthesized according to or by analogy with Synthesis Example 1, infra.

Each of the documents referred to above are incorporated herein by reference in its entirety, for all purposes. The following specific examples will provide detailed illustrations of the methods of producing and utilizing compositions of the present invention. These examples are not intended, however, to limit or restrict the scope of the invention in any way and should not be construed as providing conditions, parameters or values which must be utilized exclusively in order to practice the present invention.

EXAMPLES Example 1

The following describes a synthesis of poly(Styrene-co-methyl methacrylate-co-2-(4-vinylphenethyl)oxirane: Styrene (15 g, 144 mmol), methyl methacrylate (9.94 g, 99.3 mmol), and 2-(4-vinylphenethyl)oxirane (0.87 g, 4.99 mmol) were charged into a 250 mL three neck flask. Azobisisobutyronitrile (AIBN) (0.408 g, 2.48 mmol) and butanone (40 mL) were then added into the flask. The mixture was bubbled with N₂ for more than 30 minutes at room temperature, followed by refluxing overnight. After polymerization, the polymer solution was diluted with butanone and precipitated into 1.5 L of hexanes. The crude polymer was isolated by filtration and dried under vacuum at 45° C. overnight. The isolated polymer was redissolved in 200 mL butanone and precipitated into 1.5 L of hexanes. After filtration, the purified polymer was dried under vacuum at 45° C. overnight. 20 g polymer was obtained. Yield: 77.5%. Mw=21.0K, Mn=10.7K, pd=1.96.

Example 2

The following describes a synthesis of poly(Styrene-co-MMA-co-4-trimethylsilylethynylstyrene): Styrene (7.3 g, 70.1 mmol), methyl methacrylate (5.2 g, 51.94 mmol), and 4-trimethylsilylethynylstyrene (TMSESt) (0.7 g, 3.5 mmol) were charged into a 100 mL three neck flask. AIBN (0.204 g, 1.24 mmol) and butanone (20 mL) were then added into the flask. The mixture was bubbled with N₂ for more than 30 minutes at room temperature, followed by refluxing overnight. After polymerization, the polymer solution was diluted with butanone and precipitated into 1 L of mixed hexanes. The crude polymer was isolated by filtration and dried under vacuum at 45° C. overnight. It was re dissolved in 20 mL butanone and precipitated into 1 L of mixed hexanes. After filtration, the purified polymer was dried under vacuum at 45° C. overnight. 10 g polymer was obtained. Yield: 75.8%. Mw=28.0K, Mn=12.4K, pd=2.25.

Example 3

The following describes the synthesis of poly(Styrene-co-methyl methacrylate-co-4-ethynylstyrene): The copolymer of styrene, MMA and 4-ethynylstyrene [poly(St-co-MMA-co-ESt)] was made by deprotection of its precursor, poly(St-co-MMA-co-TMSESt). Poly(St-co-MMA-co-TMSESt) (0.6 g) was dissolved in 15 mL anhydrous THF. The polymer solution was cooled down to 0° C. with an ice/water bath. After 0.1 mL tetrahydrofuran (THF) solution of tetrabutylammonium fluoride (TBAF, 1 M) was added into the solution through a syringe, the solution was kept stirring at 0° C. for 1.5 hr. Then the polymer THF solution was poured into 500 mL methanol. The precipitated polymer was isolated by filtration. It was further purified by redissolving in 15 mL THF and precipitating into 500 mL methanol. The purified polymer was dried under vacuum at 45° C. overnight. 0.5 g polymer was obtained. Yield: 83.3%. Mw=29.8K, Mn=15.4K, pd=1.93.

Example 4

A 0.7 wt % solution in PGMEA was prepared with the polymer of Example 1 and the thermal acid generator, dodecylbenzene sulfonic acid triethylamine salt (DBSA/TEA) (5.0 wt % vs. polymers) and filtered through a 0.2 micron PTFE filter.

The above solution was spin coated at 1500 rpm on a 8-in Si wafer, and baked at 255° C./2 min. Final film thickness was 18 nm. A solution of block copolymer (PS-b-PMMA, Mn, 22k-b-22k, PD 1.03) was spin coated atop the resulting film at 1500 rpm to form a 40 nm thick film which was then annealed at 250° C. for 5 min. SEM analysis showed a clear delineation (fingerprint) between the blocks, see FIG. 1( a), indicating the neutrality of the polymer of Example 1.

Example 5

A 0.7 wt % solution in PGMEA was prepared with the polymer of Example 3 and the thermal acid generator, DBSA/TEA (5.0 wt % vs polymers) and filtered through a 0.2 micron PTFE filter.

The above solution was spin coated at 1500 rpm on a 8-in Si wafer, and baked at 255° C./2 min. Final film thickness was 18 nm. A solution of block copolymer (PS-b-PMMA, Mn, 22k-b-22k, PD 1.03) was spin coated atop the resulting film at 1500 rpm to form a 40 nm thick film which was then annealed at 250° C. for 5 min. SEM analysis showed a clear delineation between the blocks, see FIG. 1( b), indicating the neutrality of the polymer of Example 3.

Although the present disclosure has been shown and described with reference to particular examples, various changes and modifications which are obvious to persons skilled in the art to which the invention pertains are deemed to lie within the spirit, scope and contemplation of the subject matter set forth in the appended claims. 

What is claimed is:
 1. An underlayer formulation, said underlayer for promoting the formation of self assembled structures, comprising: a. a polymer comprising at least one monomer repeat unit having the structure

wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄alkyl or tri (C₁-C₄alkyl)silyl; b. at least one thermal acid generator; and c. a solvent.
 2. The formulation of claim 1, wherein the one or more thermal acid generator is chosen from a substituted or unsubstituted halogenated alkyl compound, a substituted or unsubstituted alkane sulfonate, a substituted or unsubstituted 2-nitrobenzyl sulfonic acid ester, an acid salt of a primary amine, an acid salt of a secondary amine, an acid salt of a tertiary amine, a dicarboximidyl sulfonic acid ester, or an oxime sulfonate ester.
 3. The formulation of claim 1, wherein the one or more thermal acid generator is chosen from tri-C₁-C₈-alkylammonium p-toluenesulfonate, tri-C1-C8-alkylammonium dodecylbenzenesulfonate, tri-C₁-C₈-alkylammonium perfluorobutane-1-sulfonate, tri-C₁-C₈-alkylammonium trifluoromethane-sulfonate, 1,2,3-tris(perfluoro C₁-C₈alkane sulfonyloxy) benzene, 1,2,3-tris(C₁-C₈ alkane sulfonyloxy) benzene, 1,2,3-tris(p-toluene sulfonyloxy) benzene, 4-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing.
 4. The formulation of claim 1, wherein the polymer further comprises one or more monomer repeat units chosen from C₁-C₁₀ alkyl (meth)acrylate, styrene, vinyl pyridine, butadiene, isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, itaconic acid, hydroxyethyl methacrylate, 4-hydroxystyrene, isobornyl methacrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.
 5. The formulation of claim 4, wherein the polymer is a random copolymer.
 6. The formulation of claim 1, wherein the polymer further comprises one or two monomer repeat units chosen from styrene or methyl methacrylate.
 7. A process for producing a formulation for depositing a cured underlayer for promoting the formation of self assembled structures, comprising: a. agitating a mixture, comprising i. a polymer comprising at least one monomer repeat unit having the structure

wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, m is 1-2 and R is H, C₁-C₄alkyl or tri (C₁-C₄alkyl)silyl; at least one thermal acid generator; and ii. a solvent; whereby a homogenous solution is produced; b. filtering the resulting homogeneous solution with a filter.
 8. The process of claim 7, wherein the one or more thermal acid generator is chosen from a substituted or unsubstituted halogenated alkyl compound, a substituted or unsubstituted alkane sulfonate, a substituted or unsubstituted 2-nitrobenzyl sulfonic acid ester, an acid salt of a primary amine, an acid salt of a secondary amine, an acid salt of a tertiary amine, a dicarboximidyl sulfonic acid ester, or an oxime sulfonate ester.
 9. The process of claim 7, wherein the one or more thermal acid generator is chosen from tri-C₁-C₈-alkylammonium p-toluenesulfonate, tri-C₁-C₈-alkylammonium dodecylbenzenesulfonate, tri-C₁-C₈-alkylammonium perfluorobutane-1-sulfonate, tri-C₁-C₈-alkylammonium trifluoromethane-sulfonate, 1,2,3-tris(perfluoro C₁-C₈alkane sulfonyloxy) benzene, 1,2,3-tris(C₁-C₈ alkane sulfonyloxy) benzene, 1,2,3-tris(p-toluene sulfonyloxy) benzene, 4-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing.
 10. The process of claim 7, wherein the polymer further comprises one or more monomer repeat units chosen from C₁-C₁₀ alkyl (meth)acrylate, styrene, vinyl pyridine, butadiene, isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, itaconic acid, hydroxyethyl methacrylate, 4-hydroxystyrene, isobornyl methacrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.
 11. The process of claim 10, wherein the polymer is a random copolymer.
 12. The process of claim 7, wherein the polymer further comprises one or two monomer repeat units chosen from styrene or methyl methacrylate.
 13. The process of claim 7, wherein the filter is an absolute filter having a pore size of less than 100 nm.
 14. A process for directing a multiplied pattern in a block copolymer film, said process comprising: a. providing a block copolymer having two or more spontaneously separating blocks; b. providing a substrate; c. coating, on the substrate, a first formulation for depositing a first coating and thermally curing the first coating; and d. disposing the block copolymer on at least a portion of the cured first coating; wherein the first formulation comprises (i) a polymer comprising at least one monomer repeat unit having the structure

and wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, and m is 1-2; (ii) at least one thermal acid generator; and (iii) a solvent.
 15. The process of claim 14, further comprising: e. before disposing the block copolymer, forming a pattern in the cured first coating by a lithographic process; and f. optionally, providing a second coating in the pattern from a second formulation; and thereafter rinsing with a rinse solution; wherein the second formulation comprises: (i) a polymer comprising at least one monomer repeat unit having the structure

and wherein X is a crosslinking group chosen from

and wherein n is 0-5, p is 0-5, q is 1-2, and m is 1-2; (ii) at least one thermal acid generator; and (iii) a solvent.
 16. The process of claim 15, wherein the first coating is a pinning layer and the second coating is a neutral layer.
 17. The process of claim 15, wherein the first coating is a neutral layer and the second coating is a pinning layer.
 18. The process of claim 14, wherein the first polymer further comprises at least one combination of monomer repeat units, said combination chosen from methyl (meth)acrylate and styrene, butadiene and butyl (meth)acrylate, butadiene and dimethyl siloxane, butadiene and methyl(meth) acrylate, butadiene and vinyl pyridine, isoprene and methyl(meth) acrylate, isoprene and vinyl pyridine, butyl (meth)acrylate and methyl(meth)acrylate, butyl (meth)acrylate and vinyl pyridine, hexyl(meth)acrylate and vinyl pyridine, isobutylene and butyl (meth)acrylate, isobutylene and dimethylsiloxane, isobutylene and methyl (meth)acrylate, isobutylene and vinyl pyridine, isoprene and ethylene oxide, butyl (meth)acrylate and vinyl pyridine, ethylene and methyl (meth)acrylate, methyl (meth)acrylate and butyl (meth)acrylate, styrene and butadiene, styrene and butyl (meth)acrylate, styrene and dimethylsiloxane, styrene and isoprene, styrene and vinylpyridine, ethylene and vinyl pyridine, vinyl pyridine and methyl (meth)acrylate, ethylene oxide and isoprene, ethylene oxide and butadiene, ethylene oxide and styrene, ethylene oxide and methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and butadiene, 2-hydroxyethyl (meth)acrylate and butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and dimethyl siloxane, 2-hydroxyethyl (meth)acrylate and ethylene, 2-hydroxyethyl (meth)acrylate and hexyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate and isobutylene, 2-hydroxyethyl (meth)acrylate and isoprene, 2-hydroxyethyl (meth)acrylate and styrene, 2-hydroxyethyl (meth)acrylate and vinyl pyridine, (meth)acrylonitrile and butadiene, (meth)acrylonitrile and butyl (meth)acrylate, (meth)acrylonitrile and dimethyl siloxane, (meth)acrylonitrile and ethylene oxide, (meth)acrylonitrile and ethylene, (meth)acrylonitrile and hexyl(meth)acrylate, (meth)acrylonitrile and 2-hydroxyethyl (meth)acrylate(meth), acrylonitrile and isobutylene, (meth)acrylonitrile and isoprene, (meth)acrylonitrile and methyl (meth)acrylate, (meth)acrylonitrile and styrene, or (meth)acrylonitrile and vinyl pyridine.
 19. The process of claim 15, wherein the second polymer comprises at least one monomer repeat unit chosen from C₁-C₁₀ alkyl (meth)acrylate, styrene, vinyl pyridine, butadiene, isoprene, ethylene, propylene, α-methyl styrene, itaconic anhydride, maleic anhydride, maleic acid, itaconic acid, hydroxyethyl methacrylate, 4-hydroxystyrene, isobornyl methacrylate, (meth)acrylamide, (meth)acrylonitrile, dimethyl siloxane, ethylene oxide, ethylene, 2-hydroxyethyl (meth)acrylate, or isobutylene.
 20. The process of claim 14, wherein the at least one thermal acid generator is chosen from tri-C₁-C₈-alkylammonium p-toluenesulfonate, tri-C₁-C₈-alkylammonium dodecylbenzenesulfonate, tri-C1-C8-alkylammonium perfluorobutane-1-sulfonate, tri-C₁-C₈-alkylammonium trifluoromethane-sulfonate, 1,2,3-tris(perfluoro C1-C8 alkane sulfonyloxy) benzene, 1,2,3-tris(C₁-C₈ alkane sulfonyloxy) benzene, 1,2,3-tris(p-toluene sulfonyloxy) benzene, 4-nitrobenzyl 9,10-dimethoxyanthracene-2-sulfonate, N-hydroxyphthalimide trifluoromethane-sulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate or a combination comprising at least one of the foregoing. 